An electrochemical energy storage device includes a cathode, an anode, and an electrolyte disposed between the cathode and the anode. The anode includes a capacitive material as a majority component, and further includes an electrochemically active material as a minority component, such that an operating potential of the anode is configured according to a reaction potential of the electrochemically active material.
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1. An electrochemical energy storage device comprising:
a cathode;
an anode; and
an aqueous electrolyte disposed between the cathode and the anode and having a ph less than 3,
wherein the cathode includes a material having a prussian blue crystal structure, and
wherein the anode includes a capacitive material as a majority component, and further includes an electrochemically active material as a minority component, such that an operating potential of the anode is configured according to a reaction potential of the electrochemically active material.
2. The electrochemical energy storage device of
3. The electrochemical energy storage device of
4. The electrochemical energy storage device of
5. The electrochemical energy storage device of
6. The electrochemical energy storage device of
7. The electrochemical energy storage device of
8. The electrochemical energy storage device of
9. The electrochemical energy storage device of
10. The electrochemical energy storage device of
11. The electrochemical energy storage device of
12. The electrochemical energy storage device of
13. The electrochemical energy storage device of
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This application claims the benefit of U.S. Provisional Application Ser. No. 61/529,766, filed on Aug. 31, 2011, the disclosure of which is incorporated herein by reference in its entirety.
The invention generally relates to electrochemical energy storage devices and, more particularly, electrode materials for electrochemical energy storage devices.
To a large extent, recent research and development on battery technology has involved work on various versions of lithium-ion systems, and has been focused on small- to medium-scale applications, such as portable electronics and vehicle propulsion. Much less attention has been given to energy storage problems related to the large scale electrical power grid, despite costly transient outages, a rapidly growing need for frequency regulation, and the necessity for load balancing in concert with the integration of intermittent energy sources such as solar and wind. Instead of emphasizing large values of energy density and specific energy, these grid-scale energy storage applications demand high durability (e.g., long cycle life), high short term power output (e.g., high rate), and low cost.
Current solutions to address short term, high power requirements include traditional lead-acid batteries and certain advanced battery technologies. However, lead-acid batteries have insufficient cycle life and typically cannot withstand deep discharge. Common metal hydride/nickel batteries, which have excellent cycle life, are considered to be too expensive for use on a large scale, as are the sodium/sulfur and lithium-ion systems. In addition, these battery technologies typically show significant voltage hysteresis, and thus have reduced round-trip energy efficiencies when operated at high rates.
It is against this background that a need arose to develop the electrode materials and related methods and systems described herein.
One aspect of the invention relates to an electrochemical energy storage device. In one embodiment, the device includes a cathode, an anode, and an electrolyte disposed between the cathode and the anode. The anode includes a capacitive material as a majority component, and further includes an electrochemically active material as a minority component, such that an operating potential of the anode is configured according to the reaction potential of the electrochemically active material.
In another embodiment, the device includes a first electrode, a second electrode, and an aqueous electrolyte disposed between the first electrode and the second electrode. At least one of the first electrode and the second electrode is configured as a hybrid electrode including a capacitive material and an electrochemically active material, and a weight percentage of the electrochemically active material is no greater than 40% relative to a combined weight of the electrochemically active material and the capacitive material in the hybrid electrode. The device is configured for charging to a voltage greater than 1.2 V.
In a further embodiment, the device includes a first capacitive electrode, a second capacitive electrode, and an electrolyte disposed between the first capacitive electrode and the second capacitive electrode. The first capacitive electrode includes a first additive configured to undergo a Faradaic reaction at a first reaction potential, and the second capacitive electrode includes a second additive configured to undergo a Faradaic reaction at a second reaction potential different from the first reaction potential.
Other aspects and embodiments of the invention are also contemplated, including aspects and embodiments related to methods of manufacturing and operating the batteries described herein. The foregoing summary and the following detailed description are not meant to restrict the invention to any particular embodiment but are merely meant to describe some embodiments of the invention.
For a better understanding of the nature and objects of some embodiments of the invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings.
The following definitions apply to some of the aspects described with respect to some embodiments of the invention. These definitions may likewise be expanded upon herein.
As used herein, the singular terms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to an object can include multiple objects unless the context clearly dictates otherwise.
As used herein, the term “set” refers to a collection of one or more objects. Thus, for example, a set of objects can include a single object or multiple objects. Objects of a set also can be referred to as members of the set. Objects of a set can be the same or different. In some instances, objects of a set can share one or more common properties.
As used herein, the term “adjacent” refers to being near or adjoining. Adjacent objects can be spaced apart from one another or can be in actual or direct contact with one another. In some instances, adjacent objects can be coupled to one another or can be formed integrally with one another.
As used herein, the terms “couple,” “coupled,” and “coupling” refer to an operational connection or linking. Coupled objects can be directly connected to one another or can be indirectly connected to one another, such as via an intermediary set of objects.
As used herein, the terms “substantially” and “substantial” refer to a considerable degree or extent. When used in conjunction with an event or circumstance, the terms can refer to instances in which the event or circumstance occurs precisely as well as instances in which the event or circumstance occurs to a close approximation, such as accounting for typical tolerance levels or variability of the embodiments described herein.
As used herein, the terms “optional” and “optionally” mean that the subsequently described event or circumstance may or may not occur and that the description includes instances where the event or circumstance occurs and instances in which it does not.
As used herein, the term “size” refers to a characteristic dimension of an object. Thus, for example, a size of an object that is spherical can refer to a diameter of the object. In the case of an object that is non-spherical, a size of the non-spherical object can refer to a diameter of a corresponding spherical object, where the corresponding spherical object exhibits or has a particular set of derivable or measurable properties that are substantially the same as those of the non-spherical object. Thus, for example, a size of a non-spherical object can refer to a diameter of a corresponding spherical object that exhibits light scattering or other properties that are substantially the same as those of the non-spherical object. Alternatively, or in conjunction, a size of a non-spherical object can refer to an average of various orthogonal dimensions of the object. Thus, for example, a size of an object that is a spheroidal can refer to an average of a major axis and a minor axis of the object. When referring to a set of objects as having a particular size, it is contemplated that the objects can have a distribution of sizes around the particular size. Thus, as used herein, a size of a set of objects can refer to a typical size of a distribution of sizes, such as an average size, a median size, or a peak size.
Embodiments of the invention relate to a hybrid electrode including a combination or mixture of at least one capacitive material and at least one electrochemically active material. In some embodiments, the capacitive material is a primary or majority component, and the electrochemically active material is a secondary or minority component that is included as an additive. The inclusion of the capacitive material as the majority component retains or enhances desirable properties of the capacitive material, including high rate capability and long cycle life, while the inclusion of the electrochemically active material yields a synergistic effect that allows control over an operating potential of the hybrid electrode. Specifically, by including the electrochemically active material that has a reaction potential in a desired range, the operating potential of the hybrid electrode takes on, or is shifted towards, that reaction potential, thereby allowing lowering or raising of the operating potential of the hybrid electrode. Such control over the operating potential of the hybrid electrode, in turn, allows for a higher overall voltage for an electrochemical energy storage device, such as a higher full cell voltage in the case of a battery or a higher working voltage in the case of a capacitor.
To motivate some embodiments of the invention, portions of the following discussion pertain to aqueous (i.e., water-based) electrolyte batteries, although it should be understood that the discussion also applies, or can be extended, to other types of electrochemical energy storage devices, including organic (i.e., organic solvent-based) electrolyte and ionic liquid (i.e., ionic liquid solvent-based) electrolyte batteries and capacitors, such as ultracapacitors, supercapacitors, or electric double-layer capacitors.
The development of a negative electrode (i.e., anode) material for use in aqueous electrolyte batteries is a challenging task, as the anode material should exhibit requisite levels of cyclability and chemical stability in the presence of water. Moreover, an operating potential range of an anode is bounded or constrained by a range of hydrogen evolution of water, as well as a range of oxygen evolution of water.
Certain capacitive electrode materials can exhibit requisite levels of cyclability and chemical stability in the presence of water. One example is a polarizable carbon-based material such as activated carbon, which is also sometimes referred as activated charcoal. Activated carbon is a particulate form of carbon that has a high porosity, yielding a high surface area. In some embodiments, a surface area of activated carbon (or another capacitive material) can be at least about 0.5 m2/g, at least about 1 m2/g, at least about 5 m2/g, at least about 10 m2/g, at least about 20 m2/g, at least about 30 m2/g, at least about 40 m2/g, at least about 50 m2/g, or at least about 100 m2/g, and up to about 200 m2/g, up to about 300 m2/g, up to about 400 m2/g, up to about 500 m2/g, up to about 1,000 m2/g, up to about 1,500 m2/g, or more. Rather than undergoing a Faradaic reaction, activated carbon (or another capacitive material) typically stores energy in the so-called electric double layer, and behaves like a capacitor, with a charge-discharge potential profile varying substantially linearly with a state of charge. A slope of an operating potential typically depends on a surface area of an electrode-electrolyte interface, and is typically related to a capacitance of an electrode. As a general rule of thumb, a capacitance of an electric double layer in a water-based electrolyte is about 25 μF cm−2. For applications that do not specify a low weight, using a high mass loading of activated carbon can yield a large surface area, resulting in a desirable “flat-like” profile of the operating potential.
Because cycling of activated carbon (or another capacitive material) proceeds by the formation and dispersal of a double layer of charge at an electrode surface, little or no dimensional changes occur in a bulk of the electrode material during charging and discharging, thereby affording long cycle life and high energy efficiency, as evidenced by low hysteresis in a charge-discharge potential profile. Moreover, because the double layer of charge can be reversibly and rapidly formed, activated carbon (or another capacitive material) can be operated at high rates, thereby affording high power.
To achieve these objectives, a general procedure is developed for the control of an open circuit potential and an operating potential of capacitive electrodes, such as those based on activated carbon. By including an electrochemically active material having a reaction potential in a desired range, an open circuit potential of the resulting hybrid electrode is shifted towards that reaction potential, such that the hybrid electrode cycles in the desired range. Advantages of this general procedure include one or both of the following:
1) The initial, open circuit potential of the hybrid electrode can be set to a desired value. In turn, setting the open circuit potential of the hybrid electrode allows control over an operating potential of the hybrid electrode during cycling. In the case of an anode, for example, the open circuit potential and the operating potential of the hybrid electrode can be lowered while remaining at or above a lower electrolyte decomposition potential at a particular pH. In such manner, a higher full cell voltage can be attained, while mitigating against electrolyte decomposition.
2) In addition to setting the open circuit potential, the inclusion of the electrochemically active material can yield a higher specific capacity for the hybrid electrode, relative to an electrode including activated carbon alone. For example, the electrochemically active material can be a battery electrode material that has a higher specific capacity than activated carbon. During cycling, the battery electrode material can contribute towards an overall specific capacity of the hybrid electrode, such as by undergoing a Faradaic reaction at its reaction potential. Compared to capacitive materials, certain battery electrode materials can have relatively constant reaction potentials during cycling. By including such a battery electrode material, the hybrid electrode can have more capacity available in a smaller potential range, relative to an electrode including activated carbon alone. Therefore, a resulting battery including the hybrid electrode can remain at higher voltages for a greater fraction of its discharge, resulting in higher energy and power outputs.
Certain capacitive materials can impart kinetic barriers against gas evolution, such as by reversibly adsorbing hydrogen, rather than reducing it in an irreversible, parasitic reaction that can impair energy efficiency and cycle life of a battery. Therefore, a hybrid anode including such a capacitive material can be operated in an aqueous electrolyte at voltages below the lower thermodynamic boundary shown in
By lowering an operating potential of a hybrid anode in a manner as shown in
The general procedure explained above also can be applied to raise an open circuit potential and an operating potential of a hybrid electrode, such as a hybrid cathode in the case of a battery or a high-potential, hybrid electrode in the case of a capacitor. Such raising of the operating potential can be carried out in place of, or in combination with, a lowering of an operating potential of a hybrid, counter electrode, such as a hybrid anode in the case of a battery or a low-potential, hybrid electrode in the case of a capacitor.
For example, in the case of a hybrid cathode or a high-potential, hybrid electrode, an upper limit of its operating potential range, when cycled in an aqueous electrolyte at a pH of about 0, can be in the range of about 1.4 V to about 0.8 V versus SHE, such as from about 1.3 V to about 0.9 V, from about 1.2 V to about 0.9 V, or from about 1.2 V to about 1 V. And when cycled in an aqueous electrolyte at a pH of about 1, the upper limit of its operating potential range can be in the range of about 1.3 V to about 0.7 V versus SHE, such as from about 1.2 V to about 0.8 V, from about 1.1 V to about 0.8 V, or from about 1.1 V to about 0.9 V. And when cycled in an aqueous electrolyte at a pH of about 2, the upper limit of its operating potential range can be in the range of about 1.25 V to about 0.65 V versus SHE, such as from about 1.15 V to about 0.75 V, from about 1.05 V to about 0.75 V, or from about 1.05 V to about 0.85 V. And when cycled in an aqueous electrolyte at a pH of about 3, the upper limit of its operating potential range can be in the range of about 1.2 V to about 0.6 V versus SHE, such as from about 1.1 V to about 0.7 V, from about 1 V to about 0.7 V, or from about 1 V to about 0.8 V. And when cycled in an aqueous electrolyte at a pH of about 4, the upper limit of its operating potential range can be in the range of about 1.15 V to about 0.55 V versus SHE, such as from about 1.05 V to about 0.65 V, from about 0.95 V to about 0.65 V, or from about 0.95 V to about 0.75 V. And when cycled in an aqueous electrolyte at a pH of about 7, the upper limit of its operating potential range can be in the range of about 1 V to about 0.4 V versus SHE, such as from about 0.9 V to about 0.5 V, from about 0.8 V to about 0.5 V, or from about 0.8 V to about 0.6 V.
By raising and lowering operating potentials of hybrid electrodes in a manner as shown in
In accordance with the general procedure explained above, a class of hybrid electrodes is developed that affords a combination of desirable properties, including high rate capability and long cycle life, along with an operating potential that is tunable to a desired range. To attain this combination of properties, a hybrid electrode includes a combination or mixture of at least one capacitive material and at least one electrochemically active material. In some embodiments, the capacitive material is a primary or majority component, and the electrochemically active material is a secondary or minority component that is included as an additive. A content of the additive can be less than 50%, expressed as a weight percentage of the additive relative to a combined weight of the additive and the capacitive material, such as no greater than about 49%, no greater than about 45%, no greater than about 40%, no greater than about 30%, no greater than about 20%, no greater than about 15%, no greater than about 14%, no greater than about 13%, no greater than about 12%, no greater than about 11%, or no greater than about 10%, and down to about 0.1% (or less), such as down to about 0.5%, down to about 1%, down to about 2%, down to about 3%, down to about 4%, down to about 5%, down to about 6%, down to about 7%, or down to about 8%. A mass or weight ratio of the capacitive material to the additive can be greater than 1:1, such as at least about 1.5:1, at least about 2:1, at least about 3:1, at least about 4:1, at least about 5:1, at least about 6:1, at least about 7:1, at least about 8:1, at least about 9:1, or at least about 10:1, and up to about 1000:1 (or more), such as up to about 500:1, up to about 100:1, up to about 50:1, up to about 40:1, up to about 30:1, up to about 20:1, or up to about 15:1. Depending on the particular application, an optimal content of the additive can be included to attain a stable operating potential in a desired range, while retaining fast kinetics and other desirable properties afforded by the capacitive material.
In some embodiments, two or more different capacitive materials can be included in a hybrid electrode, and, alternatively, or in conjunction, two or more different additives can be included in the hybrid electrode. In such embodiments, the percentages and ratios set forth above also apply with respect to a total weight of all capacitive materials included in the hybrid electrode, and with respect to a total weight of all additives included in the hybrid electrode. For example, a total content of all additives can be less than 50%, expressed as a weight percentage of a total weight of all additives relative to a combined weight of all additives and all capacitive materials.
In addition to activated carbon, additional examples of suitable capacitive materials include graphene, carbon nanotubes (e.g., single-walled carbon nanotubes and multi-walled carbon nanotubes), carbon aerogel, nanoporous carbon, and other polarizable materials having a relatively high surface area.
Depending on the particular application, a suitable electrochemically active material can be selected for inclusion as an additive according to its reaction potential (or its open circuit potential). Specifically, a suitable electrochemically active material can undergo a Faradaic reaction with a component of an electrolyte (e.g., a cation or an anion) at a reaction potential of interest. An as-synthesized electrochemically active material can be in a substantially fully oxidized state (e.g., substantially fully doped or intercalated), and can have a reaction potential that is higher (or lower) than a desired value. In order to tune its reaction potential to the desired value, the electrochemically active material can be converted or treated into at least a fractional charge state. Such treatment can be carried out electrochemically (e.g., charging or discharging in a cell), via chemical reduction, or both.
For example, in the case of a hybrid anode to be cycled in an aqueous electrolyte at a pH of about 0, a suitable additive can have a reaction potential in the range of about 0.3 V to about −0.6 V versus SHE, such as from about 0.2 V to about −0.6 V, from about 0.15 V to about −0.6 V, from about 0.1 V to about −0.6 V, from about 0.05 V to about −0.6 V, from about 0 V to about −0.6 V, from about 0 V to about −0.5 V, or from about 0 V to about −0.4 V. And when cycled in an aqueous electrolyte at a pH of about 1, a suitable additive can have a reaction potential in the range of about 0.25 V to about −0.65 V versus SHE, such as from about 0.15 V to about −0.65 V, from about 0.1 V to about −0.65 V, from about 0.05 V to about −0.65 V, from about 0 V to about −0.65 V, from about −0.05 V to about −0.65 V, from about −0.05 V to about −0.55 V, or from about −0.05 V to about −0.45 V. And when cycled in an aqueous electrolyte at a pH of about 2, a suitable additive can have a reaction potential in the range of about 0.2 V to about −0.7 V versus SHE, such as from about 0.1 V to about −0.7 V, from about 0.05 V to about −0.7 V, from about 0 V to about −0.7 V, from about −0.05 V to about −0.7 V, from about −0.1 V to about −0.7 V, from about −0.1 V to about −0.6 V, or from about −0.1 V to about −0.5 V. And when cycled in an aqueous electrolyte at a pH of about 3, a suitable additive can have a reaction potential in the range of about 0.15 V to about −0.75 V versus SHE, such as from about 0.05 V to about −0.75 V, from about 0 V to about −0.75 V, from about −0.05 V to about −0.75 V, from about −0.1 V to about −0.75 V, from about −0.15 V to about −0.75 V, from about −0.15 V to about −0.65 V, or from about −0.15 V to about −0.55 V. And when cycled in an aqueous electrolyte at a pH of about 4, a suitable additive can have a reaction potential in the range of about 0.1 V to about −0.8 V versus SHE, such as from about 0 V to about −0.8 V, from about −0.05 V to about −0.8 V, from about −0.1 V to about −0.8 V, from about −0.15 V to about −0.8 V, from about −0.2 V to about −0.8 V, from about −0.2 V to about −0.7 V, or from about −0.2 V to about −0.6 V. And when cycled in an aqueous electrolyte at a pH of about 7, a suitable additive can have a reaction potential in the range of about −0.1 V to about −1 V versus SHE, such as from about −0.2 V to about −1 V, from about −0.25 V to about −1 V, from about −0.3 V to about −1 V, from about −0.35 V to about −1 V, from about −0.4 V to about −1 V, from about −0.4 V to about −0.9 V, or from about −0.4 V to about −0.8 V.
As another example, in the case of a hybrid cathode to be cycled in an aqueous electrolyte at a pH of about 0, a suitable additive can have a reaction potential in the range of about 1.4 V to about 0.6 V versus SHE, such as from about 1.3 V to about 0.7 V, from about 1.2 V to about 0.7 V, or from about 1.2 V to about 0.8 V. And when cycled in an aqueous electrolyte at a pH of about 1, a suitable additive can have a reaction potential in the range of about 1.3 V to about 0.5 V versus SHE, such as from about 1.2 V to about 0.6 V, from about 1.1 V to about 0.6 V, or from about 1.1 V to about 0.7 V. And when cycled in an aqueous electrolyte at a pH of about 2, a suitable additive can have a reaction potential in the range of about 1.25 V to about 0.45 V versus SHE, such as from about 1.15 V to about 0.55 V, from about 1.05 V to about 0.55 V, or from about 1.05 V to about 0.65 V. And when cycled in an aqueous electrolyte at a pH of about 3, a suitable additive can have a reaction potential in the range of about 1.2 V to about 0.4 V versus SHE, such as from about 1.1 V to about 0.5 V, from about 1 V to about 0.5 V, or from about 1 V to about 0.6 V. And when cycled in an aqueous electrolyte at a pH of about 4, a suitable additive can have a reaction potential in the range of about 1.15 V to about 0.35 V versus SHE, such as from about 1.05 V to about 0.45 V, from about 0.95 V to about 0.45 V, or from about 0.95 V to about 0.55 V. And when cycled in an aqueous electrolyte at a pH of about 7, a suitable additive can have a reaction potential in the range of about 1 V to about 0.2 V versus SHE, such as from about 0.9 V to about 0.3 V, from about 0.8 V to about 0.3 V, or from about 0.8 V to about 0.4 V.
As a further example, in the case of a hybrid cathode or a high-potential, hybrid electrode to be cycled in an organic electrolyte, a suitable additive can have a reaction potential in the range of about 0.5 V (or less) to about 5 V (or more) versus SHE, such as from about 0.6 V to about 5 V, from about 0.7 V to about 5 V, from about 0.8 V to about 5 V, from about 0.9 V to about 5 V, from about 1 V to about 5 V, from about 1.5 V to about 5 V, from about 2 V to about 5 V, from about 2.5 V to about 5 V, from about 3 V to about 5 V, from about 0.7 V to about 4.9 V, from about 0.7 V to about 4.7 V, from about 0.7 V to about 4.5 V, from about 0.7 V to about 4.3 V, from about 0.7 V to about 4.1 V, from about 0.7 V to about 3.9 V, from about 0.7 V to about 3.7 V, from about 0.7 V to about 3.5 V, from about 0.7 V to about 3.3 V, or from about 0.7 V to about 3.1 V.
Examples of suitable additives include electronically conductive polymers that can undergo a doping/de-doping reaction with a component of an electrolyte at a desired reaction potential, such as nitrogen-containing aromatic polymers (e.g., polypyrroles, polycarbazoles, polyindoles, polyanilines, and polyazepines), sulfur-containing aromatic polymers (e.g., poly(3,4-ethylenedioxythiophene)), polythiophenes, polyfluorenes, polyphenylenes, polypyrenes, polyazulenes, polynapthalenes, polyacetylenes, and poly(p-phenylene vinylene).
Additional examples of suitable additives include lithium-ion intercalation materials that can undergo an intercalation/de-intercalation reaction with lithium ions at a desired reaction potential, such as lithium transition metal oxides (e.g., lithium manganese oxide (LiMn2O4), lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), lithium titanium oxide (Li4Ti5O12), LiCo1/3Ni1/3Mn1/3O2, and Li(LiaNixMny Coz)O2), lithium transition metal phosphates (e.g., lithium titanium phosphate (LiTi2(PO4)3)) and lithium iron phosphate (LiFePO4)), and lithium transition metal fluorophosphates (e.g., lithium iron fluorophosphate (Li2FePO4F)).
Additional examples of suitable additives include intercalation materials that can undergo an intercalation/de-intercalation reaction with other ions different from lithium ions at a desired reaction potential, such as ions having a larger crystallographic diameter than lithium ions. Such intercalation materials include sodium-ion intercalation materials, such as transition metal oxides (e.g., tungsten oxide (WO3) and vanadium oxide (V2O5)) and sodium transition metal oxides (e.g., sodium manganese oxide (Na4Mn9O18)), and potassium-ion intercalation materials, such as transition metal oxides (e.g., tungsten oxide (WO3) and vanadium oxide (V2O5)).
Further examples of suitable additives include a class of electrochemically active materials having stiff open framework structures into which hydrated cations can be reversibly and rapidly intercalated from aqueous electrolytes or other types of electrolytes. In particular, open framework structures with the Prussian Blue-type hexacyanometallate crystal structure afford advantages including greater durability and faster kinetics when compared to other intercalation and displacement electrode materials. A general formula for this class of materials is given by:
AxPy[R(CN)6-wLw]z.(H2O)n (I)
where
A material given by formula (I) can include A, P, R, CN, L, and H2O, such that molar ratios of A, P, [R(CN)6-wLw], and H2O can be represented as A:P:[R(CN)6-wLw]:H2O=x:y:z:n, molar ratios of P and [R(CN)6-wLw] can be represented as P:[R(CN)6-wLw]=y:z, molar ratios of P and R can be represented as P:R=y:z, molar ratios of P and CN can be represented as P:CN=y:(6−w)·z, and molar ratios of P and L can be represented as P:L=y:w·z. In the case w=0, molar ratios of A, P, and [R(CN)6] can be represented as A:P:[R(CN)6]=x:y:z, molar ratios of P and [R(CN)6] can be represented as P:[R(CN)6]=y:z, molar ratios of P and R can be represented as P:R=y:z, and molar ratios of P and CN can be represented as P:CN=y:6z.
In some embodiments, a crystal structure of a material given by formula (I) is analogous to that of the ABX3 perovskites, with Pm+ and Rn+ cations in an ordered arrangement upon “B” sites. The occupancy of the tetrahedrally-coordinated “A” sites in the large cages in this crystallographically porous framework can vary from x=0 to x=2, with corresponding changes in the valence of one or both of the P and R species. As a result, such a material becomes a mixed ionic-electronic conductor. The insertion of a species of appropriate size into the “A” sites can be performed electrochemically with rapid kinetics. Specifically and in view of this crystallographically porous framework, a number of different hydrated cations can readily move into and out of the “A” sites. The species that is reversibly inserted from an electrolyte also can be exchanged, thereby allowing the implementation of electrodes in hybrid-ion aqueous electrolyte batteries. In some embodiments, a reaction potential range is at least partly determined by the identities of the A, P, and R species, and therefore can be adjusted or modified by changing their identities. For example, a reaction potential can decrease with increasing Stokes ionic diameter of the A species, and can increase with an effective ionic diameter of the A species.
Referring to formula (I), examples of suitable A cations include: (1) H+; (2) alkali metal cations (e.g., Li+, Na+, K+, Rb+, and Cs+); (3) polyatomic, monovalent cations (e.g., NH4+); (4) alkaline earth metal cations (e.g., Be2+, Mg2+, Ca2+, Sr2+, and Ba2+); and (5) polyatomic, divalent cations. In some embodiments, selection of a suitable A cation can be based on a size of the A cation relative to a size of interstitial sites and channels between the sites within the Prussian Blue crystal structure, which can be represented as a void having a diameter of about 3.5 Å. Because the A cation is typically hydrated in an aqueous electrolyte, it would be expected that a Stokes ionic diameter is the relevant measure of the size of the hydrated A cation, and thus a Stokes ionic diameter of about 3.5 Å is expected to represent an upper size limit for the A cation. Surprisingly, certain materials given by formula (I) also can accommodate A cations having a Stokes ionic diameter greater than 3.5 Å, albeit having an effective ionic diameter (e.g., a crystallographic diameter or other measure of size in the substantial absence of hydration) within, or no greater than, about 3.5 Å. Examples of A cations having a Stokes ionic diameter greater than 3.5 Å include Li+, Na+, Mg2+, Ca2+, and Ba2+. The flexibility in accommodating such A cations affords a number of advantages, such as in terms of the selection of a desired reaction potential range and improved kinetics, as well as facilitating the implementation of hybrid-ion aqueous electrolyte batteries and affording cost advantages. Selection of a suitable hydrated A cation also can be based on a size of the A cation relative to a size of channels between interstitial sites.
Still referring to formula (I), examples of suitable P and R metal cations include: (1) cations of transition metals, such as top row (or row 4) transition metals (e.g., Ti, Va, Cr, Mn, Fe, Co, Ni, Cu, and Zn), row 5 transition metals (e.g., Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, and Cd), and other transition metals; (2) post-transition metals (e.g., Al, Ga, In, Sn, Tl, Pb, and Bi); (3) metalloids (e.g., B, Si, Ge, As, Sb, Te, and Po); and (4) lanthanides (e.g., La and Ce). In some embodiments, selection of a suitable P metal cation can be based on the metal cation having the capability to take on different oxidation states. Top row (or row 4) transition metals are examples of metals that can take on a variety of oxidation states. In some embodiments, selection of a suitable R metal cation can be based on the metal cation having the capability to take on different oxidation states, chemical stability of the hexacyanometallate group R(CN)6, or a combination of these considerations. Fe, Mn, Cr, and Co are examples of metals that form stable hexacyanometallate groups. Examples of suitable L anions include monovalent anions, such as polyatomic, monovalent anions (e.g., NO− and CO−). In some embodiments, selection of a suitable L anion can be based on chemical stability of its bonding with the R metal cation within the group [R(CN)6-wLw].
Additional examples of suitable cations for A, P, and R can be categorized in terms of their valency and include: (1) monovalent cations (e.g., Ag+, Cu+, Li+, Na+, K+, Hg+, Tl+, NH4+); (2) divalent cations (e.g., Mg2+, Ca2+, Sn2+, Sr2+, Ba2+, Zn2+, Cd2+, Fe2+, Mn2+, Cu2+, Ni2+, Co2+, Pb2+, Cr2+, Hg2+, Os2+, Pd2+, Rh2+, Ru2+, Ti2+, Th2+, and V2+); (3) trivalent cations (e.g., Al3+, Bi3+, Ce3+, Co3+, Cr3+, Cu3+, Fe3+, In3+, Ir3+, La3+, Mn3+, Mo3+, Nb3+, Ni3+, Os3+, Rh3+, Ru3+, Sb3+, Ta3+, Ti3+, V3+, and Y3+); and (4) tetravalent cations (e.g., Ce4+, Cu4+, Cr4+, Fe4+, Ge4+, Mn4+, Nb4+, Ni4+, Pb4+, Ru4+, Si4+, Sn4+, Ta4+, Te4+, Ti4+, V4+, W4+, and Zr4+).
Specific examples of materials given by formula (I) include:
In formula (I), a mixture of different species can be included for any one or more of A, P, R, and L, such that formula (I) can be further generalized by: (1) representing A as Ax-a′A′a′ or Ax-a′-a″ . . . A′a′A″a″ . . . ; (2) representing P as Py-p′P′p′ or Py-p′-p″ . . . P′p′P″p″ . . . ; (3) representing R as R1-r′R′r′ or R1-r′-r″ . . . R′r′R″r″ . . . ; and (4) representing L as Lw-l′L′l′ or Lw-l′-l″ . . . L′l′L″l″ . . . . In the generalized version of formula (I), the different species for A can correspond to the same chemical element with different oxidation states, different chemical elements, or a combination thereof. Likewise, the different species for each of P, R, and L can correspond to the same chemical element with different oxidation states, different chemical elements, or a combination thereof.
Various materials given by formula (I) can be synthesized using a spontaneous, bulk precipitation approach with low cost precursors, and the synthesis can be readily scaled up for applications such as grid-scale energy storage. For example, synthesis can be carried out by combining chemical precursors or other sources of A, P, R, CN, and L in an aqueous solution or another type of medium, with the precursors reacting spontaneously to form a powder product. In some embodiments, the chemical precursors can include a source of P (e.g., a salt of P) and a source of A and R(CN)6 (e.g., a salt of A and R(CN)6 such as A3R(CN)6). Synthesis can be carried out by co-precipitation, with substantially simultaneous dropwise addition of the precursors to a common liquid medium to maintain a substantially constant ratio of the precursors (e.g., a molar ratio of about 2:1 for the source of P and the source of A and R(CN)6, or another molar ratio m:1 with m≧1, such as m>1 or m≧1.5) and to provide a consistent composition of a precipitate. Heating can be carried out, such as to a temperature above room temperature and below about 100° C. (e.g., in the range of about 40° C. to about 99° C., about 50° C. to about 90° C., or about 60° C. to about 80° C.), to yield better crystallinity in the final product, and an acid or a base also can be added to the reaction mixture to inhibit side reactions. A particular A used during synthesis can be exchanged by a different A′ for implementation within a battery, thereby affording advantages such as the selection of a desired electrode potential range.
The resulting powder product can include particles having a grain size (e.g., an average or median grain size) no greater than about 10 μm, no greater than about 5 μm, no greater than about 1 μm, no greater than about 900 nm, no greater than about 800 nm, no greater than about 700 nm, no greater than about 600 nm, no greater than about 500 nm, no greater than about 400 nm, no greater than about 300 nm, no greater than about 200 nm, or no greater than about 100 nm, and down to about 20 nm, down to about 10 nm, down to about 5 nm, or less. Without wishing to be bound by a particular theory, small grain sizes can contribute towards improved kinetics and other desirable properties, such as by affording higher surface to volume ratios.
For implementation within a battery or a capacitor, a capacitive material can be combined with an additive to form a mixture, and this mixture can be incorporated as an active material (e.g., about 90% by total weight) by mixing with a binder (e.g., about 10% by total weight) to form a slurry. Reduction of the additive to a desired charge state can occur prior, or subsequent, to forming the slurry. The resulting slurry can be deposited adjacent to a substrate, dried to form a coating, a film, or other layer adjacent to the substrate, and then assembled as a hybrid electrode. Examples of suitable binders include polyvinylidene fluoride and other types of polymeric binders. A thickness of the coating (including the active material) can be at least about 500 nm, at least about 1 μm, at least about 10 μm, at least about 20 μm, at least about 30 μm, at least about 40 μm, or at least about 50 μm, and up to about 150 μm, up to about 200 μm, up to about 300 μm, up to about 500 μm, or more. A mass loading of the active material within the resulting electrode can be at least about 500 μg/cm2, at least about 700 μg/cm2, at least about 1 mg/cm2, at least about 2 mg/cm2, at least about 3 mg/cm2, at least about 4 mg/cm2, or at least about 5 mg/cm2, and up to about 10 mg/cm2, up to about 15 mg/cm2, up to about 20 mg/cm2, up to about 30 mg/cm2, up to about 50 mg/cm2, up to about 100 mg/cm2, or more.
The hybrid electrodes described herein can be used for a variety of batteries, capacitors, and other electrochemical energy storage devices. For example, the hybrid electrodes can be substituted in place of, or used in conjunction with, conventional electrodes for aqueous electrolyte batteries, organic electrolyte batteries, aqueous electrolyte capacitors, and organic electrolyte capacitors.
In the illustrated embodiment, at least one of the electrodes 102 and 104 is primarily capacitive in nature, and is formed as a hybrid electrode including a capacitive material, which is present as a majority component, and an electrochemically active material, which is present as an additive. For example, the electrode 104 can be formed as a hybrid anode, while the electrode 102 can be formed as a cathode that is primarily or substantially Faradaic in nature, such as formed using a material given by formula (I) or another electrochemically active material, with little or no capacitive material included. As another example, the electrode 102 can be formed as a high-potential, hybrid electrode including one type of additive having a relatively high reaction potential, and the electrode 104 can be formed as a low-potential, hybrid electrode including another type of additive having a relatively low reaction potential.
The inclusion of a hybrid electrode (or a pair of hybrid electrodes) in the device 100 yields a number of desirable properties, including high efficiency, long cycle life, high rate capability, and high voltage operation.
For example, in terms of round-trip energy efficiency at a rate of 10 C (or another reference rate higher or lower than 10 C, such as 0.83 C, 5 C, 8.3 C, 17 C, 42 C, 50 C, or 83 C), the device 100 can have an energy efficiency (e.g., an initial or maximum energy efficiency or an average energy efficiency over a particular number of cycles, such as cycles 1 through 100 or cycles 1 through 1,000) that is at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 98%, and up to about 99%, up to about 99.5%, up to about 99.9%, or more.
As another example, the device 100 can exhibit excellent retention of specific capacity over several charging and discharging cycles, such that, after 1,000 cycles to full discharge at a rate of 10 C (or another reference rate higher or lower than 10 C, such as 0.83 C, 5 C, 8.3 C, 17 C, 42 C, 50 C, or 83 C), at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 98%, and up to about 99%, up to about 99.5%, up to about 99.9%, or more of an initial or maximum specific capacity is retained, and, after 10,000 cycles to full discharge at a rate of 10 C (or another reference rate higher or lower than 10 C, such as 0.83 C, 5 C, 8.3 C, 17 C, 42 C, 50 C, or 83 C), at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least about 93%, and up to about 99%, up to about 99.5%, up to about 99.9%, or more of an initial or maximum specific capacity is retained. Likewise, the device 100 can exhibit excellent retention of round-trip energy efficiency over several charging and discharging cycles, such that, after 1,000 cycles or even after 10,000 cycles to full discharge at a rate of 10 C (or another reference rate higher or lower than 10 C, such as 0.83 C, 5 C, 8.3 C, 17 C, 42 C, 50 C, or 83 C), at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 98%, and up to about 99%, up to about 99.5%, up to about 99.9%, or more of an initial or maximum energy efficiency is retained.
As another example, the device 100 can exhibit excellent retention of specific capacity when cycled at high rates, such that, when cycled at a rate of 10 C (or another rate that is ten times a reference rate), at least about 65%, at least about 70%, at least about 75%, at least about 80%, or at least about 85%, and up to about 90%, up to about 95%, up to about 99%, or more of a maximum specific capacity or a low rate, reference specific capacity (e.g., at the reference rate of 5 C, 1 C, 0.83 C, C/5, or C/10) is retained, and, when cycled at a rate of 50 C (or another rate that is fifty times the reference rate), at least about 15%, at least about 20%, at least about 25%, at least about 30%, or at least about 35%, and up to about 60%, up to about 70%, up to about 80%, or more of a maximum specific capacity or a low rate, reference specific capacity (e.g., at the reference rate of 5 C, 1 C, 0.83 C, C/5, or C/10) is retained. Likewise, the device 100 can exhibit excellent retention of round-trip energy efficiency when cycled at high rates, such that, when cycled at a rate of 10 C (or another rate that is ten times a reference rate), at least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least about 95%, and up to about 99%, up to about 99.5%, up to about 99.9%, or more of a maximum energy efficiency or a low rate, reference energy efficiency (e.g., at the reference rate of 5 C, 1 C, 0.83 C, C/5, or C/10) is retained, and, when cycled at a rate of 50 C (or another rate that is fifty times the reference rate), at least about 60%, at least about 65%, at least about 70%, at least about 75%, or at least about 80%, and up to about 90%, up to about 95%, up to about 99%, or more of a maximum energy efficiency or a low rate, reference energy efficiency (e.g., at the reference rate of 5 C, 1 C, 0.83 C, C/5, or C/10) is retained.
The following examples describe specific aspects of some embodiments of the invention to illustrate and provide a description for those of ordinary skill in the art. The examples should not be construed as limiting the invention, as the examples merely provide specific methodology useful in understanding and practicing some embodiments of the invention.
This example describes an aqueous potassium-ion battery. A cathode of the device includes copper hexacyanoferrate (“CuHCF”), one of the Prussian Blue analogues that exhibit long cycle life and high rate. An anode of the device is a member of a class of hybrid electrodes that include an electrochemically active additive, which enhances the performance of a capacitive material. The particular anode reported in this example combines an electrochemically active polymer, namely polypyrrole (“PPy”), and activated carbon (“AC”) in a hybrid electrode that provides the high rate capability of an ultracapacitor and a well-defined electrochemical potential of a battery electrode. The resulting full cell has high power and energy efficiency, and lasts for thousands of cycles.
CuHCF has the open framework Prussian Blue crystal structure (see
2KxCuy[FeIII(CN)6]+a(K++e−)=2Kx-aCuy[FeIII(CN)6]1-a[FeII(CN)6]a
This reaction occurs at about 0.95 V (mid-composition) versus SHE, which is desirable for a cathode in mildly acidic aqueous electrolytes. Full electrochemical cycling of CuHCF results in a specific capacity of about 60 mAh/g. This reaction proceeds by the insertion of K+ into the “A” sites with substantially no changes in the framework structure. Here, highly crystalline, 20-50 nm CuHCF nanoparticles (see
The use of the CuHCF cathode places certain conditions on the properties of the anode. The anode should be chemically stable in acidic solutions (pH=1-2) and should have an operating potential near −0.1 V versus SHE, the thermodynamic limit for water decomposition in this pH range. In addition, the anode should have a long cycle life and a high rate capability. The use of K+ as the insertion ion for CuHCF, and its potential sensitivity to other alkali ions such as Li+ and Na+ place further conditions on the properties of the anode.
AC is an electric double-layer capacitor (“EDLC”) electrode material that fulfills certain compatibility conditions and can be successfully paired with CuHCF. EDLCs can operate in a variety of aqueous and organic electrolytes, and can have high specific power and long cycle life. However, the cycling of an EDLC electrode typically proceeds by the physical formation and dispersal of a double layer of charge at the electrode surface, with substantially no Faradaic reaction of the bulk electrode material. This mechanism can result in a low specific capacity and deleterious self-discharge. An operating potential of a capacitive electrode can vary substantially linearly with its charge state in a steep discharge profile, so the capacitive electrode can be restricted in offering useful energy and power at shallow discharge. In addition, in the case of AC, negatively charged surface groups that improve hydrophilicity also can raise the open circuit potential (“OCP”) of AC in aqueous electrolytes to above about 0.3 V versus SHE, which can be too high for a useful anode paired with a CuHCF cathode. One benefit of using AC as an anode in aqueous electrolytes is its kinetic suppression of H2 evolution at low potentials, but its low specific capacity, steep discharge profile, and high OCP place restrictions on its practicality.
PPy is a member of a class of electronically conductive polymers, and includes multiple connected pyrrole ring (“Py”) structures. PPy has a high theoretical specific capacity, and is very insoluble in aqueous electrolytes, which allow it to be paired with CuHCF. Electrochemical cycling of PPy proceeds by a p-type doping/de-doping reaction that can be represented as:
##STR00001##
Anions (I−) from an electrolyte coordinate to PPy chains during oxidation (doping), and the anions are released during reduction (de-doping). The mid-composition reaction potential of PPy depends on the particular doping anion, but is typically near about 0 V versus SHE, making PPy desirable for use as an anode in aqueous cells (see
A desirable anode for use with CuHCF would combine the fast kinetics of AC at the low reaction potential of reduced (e.g., fully reduced) PPy. Advantageously, this combination of properties can be achieved by intimately mixing AC with reduced PPy in a single electrode. The resulting hybrid electrode has an OCP at the well-defined doping/de-doping potential of PPy, but retains the high rate capability of AC. Without wishing to be bound by a particular theory, this shift in OCP occurs because an OCP of AC (or another EDLC electrode material) depends on the charge state of its surface, and, as a small charge capacity is associated with that state, AC in electrical contact with a material with a well-defined redox couple will take on the potential of that couple. So, in the case of an AC/PPy hybrid electrode, the OCP of the hybrid electrode corresponds to the reaction potential of the PPy component.
As-synthesized PPy powder is fully oxidized (fully doped), and has a relatively high OCP of about 0.5 V versus SHE. An electrode including doped PPy and AC will also have a high OCP, as explained above. Using a technique for chemical reduction of PPy powder by NaBH4, electrodes containing both AC and PPy were reduced, resulting in an OCP of about −0.1 V versus SHE (see
Hybrid AC/PPy electrodes have properties intermediate between pure AC and pure PPy electrodes. As the fractional PPy content of a hybrid electrode increases, the voltage hysteresis observed during cycling at a 1 C rate increases (see
When implementing a full cell with a CuHCF cathode and an AC/PPy hybrid anode, additional considerations can be addressed. First, the two electrodes in a full cell should have appropriate relative initial charge states. The AC/PPy anode was chemically reduced so that its OCP at full discharge was substantially equal to the reaction potential of fully reduced PPy. Syntheses of CuHCF typically results in a material with a fractional initial charge state because fully oxidized CuHCF has a high enough potential that it can be reduced by water. To address this issue, a reductive titration technique was developed to controllably reduce CuHCF to a desired oxidation state and OCP using Na2S2O3 (see
2KxCuy[FeIII(CN)6]+2Na2S2O3+2K+→2K1+x Cuy[FeII(CN)6]2+Na2S4O6+2Na+
Before the addition of any Na2S2O3, CuHCF is about 80% charged, so the addition of Na2S2O3 in a ratio of Na2S2O3:CuHCF of 0.8 results in full reduction. CuHCF can intercalate both K+ and Na+, but it reacts with K+ at a higher potential than it does with Na+. Though both K+ and Na+ are present during the reductive titration, CuHCF selectively intercalates K+ because of its higher equilibrium reaction potential, and OCPs observed after chemical reduction correspond to the reaction potential of CuHCF observed at the same charge state during electrochemical cycling. Electrochemical reduction of CuHCF and other Prussian Blue analogues results in a decrease in lattice parameter, as the iron-carbon bond in Fe(CN)6 shortens by about 0.05 Å during reduction. A similar decrease in the lattice parameter of CuHCF was observed during reductive titration, confirming that K+ intercalation occurred (see
Another consideration for a full cell using CuHCF and AC/PPy electrodes is the disparity in the specific capacities of the electrodes. The double layer capacitance in aqueous electrolytes is typically about 10-50 μF/cm2, so EDLCs are typically cycled over wide potential ranges to achieve appreciable capacity. However, aqueous batteries can have voltages that are restricted by water decomposition. A flat full cell voltage profile is desirable because energy scales with voltage, and power scales with the square of the voltage. If the voltage varies greatly with charge state, some of the charge is available at voltages too low to provide practical energy and power. Therefore electrodes in aqueous batteries should be cycled over relatively narrow potential ranges so that the full discharge of the devices produces usable energy. In the case of capacitive electrodes, the same charge can be accessed in a smaller potential window if a larger exposed surface, and, therefore, a larger mass is used. The CuHCF versus AC/PPy cells described here included a 10 mg/cm2, 1 cm2 CuHCF cathode and a 50 mg/cm2, 2 cm2 AC/PPy anode, resulting in a cathode/anode mass loading ratio of 1:10. Other cathode/anode mass loading ratios are contemplated, such as in the range of about 1:2 to about 1:100, such as from about 1:5 to about 1:50 or from about 1:5 to about 1:20.
A further consideration for a full cell is the electrolyte, which should be designed to allow reversible cycling of both electrodes. In the full cells reported here, CuHCF was found to be most chemically stable at pH=1.
Full cell cycling with potential cutoffs of about 0.85 V and about 1.1 V for the CuHCF cathode resulted in a full cell voltage range of about 1.4 V to about 0.9 V (see
The high capacity retention and rate capability of the CuHCF versus AC/PPy full cells result in high specific power. The average specific power during discharge at a 10 C rate during cycling between 1.4 V and 0.9 V was about 45 W/kg on the basis of the electrode masses, and a maximum specific power of nearly about 100 W/kg was achieved at 20 C. The specific energy of the cells reported here was about 5 Wh/kg. However, as the discharge voltage was bounded by 0.9 V, substantially all of the specific energy of the cells can be practically used. The specific power and energy of the CuHCF versus AC/PPy cells are constrained by the high mass loading of the anode. Reducing the anode mass loading by 50%, such as by using AC with a higher specific surface area, would nearly double the specific energy and power. Also, the cells reported here used a flooded geometry that resulted in electrolyte resistance. The use of pressed cells would further improve energy efficiency and specific power at high cycling rates.
The specific power and specific energy of the CuHCF versus AC/PPy cells are compared to other battery technologies in the Ragone plot in
By way of summary, aqueous potassium-ion batteries using an open framework CuHCF cathode and a controllable-potential capacitive anode were demonstrated to have long cycle life, high rate capability, and high efficiency. The CuHCF cathode is synthesized by a scalable, room-temperature chemical co-precipitation method. The anode combines AC with PPy, which can be synthesized in bulk near room temperature. The electrodes operate in safe, inexpensive aqueous electrolytes. The performance, scalability, and safety of these cells make them desirable for stationary storage applications including the smoothing of intermittent solar and wind power. The addition of electrochemically active additives with well-defined potentials to capacitive electrodes can be expanded to a wide variety of devices in which one or both of the electrodes is of the capacitive type, including devices using one or two EDLC/additive hybrid electrodes.
Experimental Procedures:
Preparation of nanoparticulate CuHCF was carried out according to a similar procedure as set forth in Wessells et al., “Copper hexacyanoferrate battery electrodes with long cycle life and high power,” Nat Commun 2, 550 (2011), the disclosure of which is incorporated herein by reference in its entirety. Briefly, substantially equal volumes of 40 mM Cu(NO3)2 (Alfa Aesar) and 20 mM K3Fe(CN)6 (Sigma Aldrich) were combined by simultaneous, dropwise addition into water under vigorous stirring. An excess of Cu+2 is desirable for precipitation and particle growth. Substantially all of the Fe(CN)6 is oxidized initially, but fully charged CuHCF has a potential high enough to oxidize water. Thus, spontaneous partial reduction of CuHCF occurs, resulting in a fractional initial charge state, typically between 50% and 80% charged. Five minutes after complete addition of the CuHCF precursors, 0.1 M Na2S2O3 was added until a desired molar ratio of FeIII(CN)6−3 to S2O3−2 was reached. The color of CuHCF changed from a dingy yellow to a deep claret upon addition of Na2S2O3, indicating a successful reduction. The CuHCF was filtered, washed with water, and dried in vacuum at room temperature. Slurries including CuHCF, amorphous carbon (Super P Li), poly(vinylidene)difluoride (PVDF, Kynar HSV900), and graphite (Timcal KS6) in a mass ratio of 80:9:9:2 were prepared by grinding these materials by hand, and then dispersing them in 1-methyl-2-pyrrolidinone (“NMP”). Electrodes with mass loadings of about 10 mg/cm2 CuHCF were prepared by spreading the slurry on a carbon cloth current collector (Fuel Cell Earth). The electrodes were dried in vacuum at about 60° C. for about 1 h.
PPy was prepared by chemical oxidative polymerization of its corresponding monomer (pyrrole) in an aqueous medium according to a similar procedure as set forth in Blinova et al., “Polyaniline and polypyrrole: A comparative study of the preparation,” European Polymer Journal 43, 2331-2341 (2007), the disclosure of which is incorporated herein by reference in its entirety. Pyrrole (0.03 mol, 2 ml) was dispersed in 150 ml of de-aerated (N2) cold water (0° C.). Anhydrous Na2S2O8 (oxidant) (6.61 g, 0.03 mol) was dissolved in 50 ml of cold (0° C.) water in a reaction vessel including a magnetic stirring bar and added dropwise into the stirred pyrrole solution. The reaction was carried out for about 8 h at about 0° C. with moderate stirring. The precipitated PPy was filtered off, washed with distilled water, and dried in vacuum at about 60° C. for about 8 h. The black PPy slurries including about 10% wt./wt. PVDF and about 90% wt./wt. active material, with AC and PPy in a desired mass ratio, were prepared in NMP. Electrodes with mass loadings of about 50 mg/cm2 were prepared by the procedure used for the CuHCF electrodes.
Chemical reduction of PPy was carried out by immersing the electrodes for about 20 min in a 0.1 M solution of NaBH4, according to a similar procedure as set forth in Bengoechea et al., “Chemical reduction method for industrial application of undoped polypyrrole electrodes in lithium-ion batteries,” J. Power Sources 160, 585-591 (2006), the disclosure of which is incorporated herein by reference in its entirety. The reduction can also be performed on the raw PPy powder, but may lead to material degradation if stored in air.
Flooded full cells including a CuHCF cathode, an AC/PPy anode, a 1 M potassium phosphate buffer at pH=1, and an Ag/AgCl reference electrode were prepared in a nitrogen glovebox. The AC/PPy electrode is sensitive to oxidation, so the cell should be kept oxygen free to achieve efficient anode cycling at potentials below the SHE.
The approach reported in this example is to use a mixture of PPy and AC in order to reduce or otherwise control an OCP of the AC. In the resulting hybrid electrode, the two materials are electrically coupled and, therefore, take on a substantially common potential: a potential of a doping/de-doping reaction of the PPy. This allows the AC to cycle at a desired potential (or within a desired potential range) by adding a non-capacitive or pseudo-capacitive contribution. Moreover, the use of AC can provide further advantages by reaching potentials below the thermodynamic value for hydrogen evolution, due to a mechanism of reversible adsorption-desorption of H atoms. The approach of using PPy is demonstrated here, and, in principle, the approach can be applied to any electrochemically active material that can be mixed with a capacitive material and galvanostatically cycled.
PPy was synthesized by modifying a procedure as set forth in Stejskal et al., “Polyaniline and polypyrrole prepared in the presence of surfactants: a comparative conductivity study,” Polymer 44, 1353-1358 (2003), the disclosure of which is incorporated herein by reference in its entirety. Pyrrole (0.03 mol, 2 ml) was dispersed in 150 ml of de-aerated (by N2 bubbling) cold water (0° C.) in a reaction vessel including a magnetic stirring bar. Anhydrous (NH4)2S2O8 (an oxidant) (6.61 g, 0.03 mol) was dissolved in 50 ml of cold (0° C.) water and added dropwise into the PPy dispersion. The reaction was carried out for about 8 h at about 0° C. (ice bath) with moderate stirring. Precipitated PPy was filtered off and washed thoroughly with cold de-ionized water. The resulting black PPy powder was dried in vacuum at about 60° C. for about 2 h. The synthesis of PPy can be modified to produce product powders of varying particle size and morphology, and varying crystallinity, by varying the temperature of the synthesis reaction, and the relative and absolute concentrations of the precursor reactants. Devices using AC/PPy electrodes have been demonstrated for a variety of PPy synthesis conditions.
A cyclic voltammogram (“CV”) of a PPy electrode prepared by drop casting an ink (80% wt./wt. PPy—10% wt./wt. PVDF—10% wt./wt. carbon black) onto a carbon cloth is shown in
An OCP of an AC electrode can depend on the presence of specific groups at its surface, but typically is near about 0.4 V to about 0.6 V versus SHE. Such an OCP can be too high for use as an anode in an aqueous electrolyte, because the anode operating potential should be close to a hydrogen evolution potential (e.g., about 0 V versus SHE at pH=0). A desirable anode would combine the fast kinetics of AC at the low reaction potential of PPy. In
This example demonstrates that an AC/PPy electrode can be operated against other types of electrodes, in addition to Prussian Blue analogue electrodes. Specifically, this example describes an aqueous lithium-ion battery. A cathode of the device is composed of a slurry of an electrochemically active lithium manganese oxide (LiMn2O4), carbon black, and a polymer binder, and is cycled against an AC/PPy anode in an aqueous 6 M LiNO3 electrolyte at a neutral pH (pH=7). As shown in
The LiNO3 electrolyte in this example includes a different cation, a different anion, and a different pH than the potassium phosphate buffer used in full cells of certain other examples herein. This example demonstrates the ability to use the AC/PPy electrode in a wide variety of aqueous salt electrolytes over a wide pH range. Further, this example demonstrates that a wide variety of electrodes (e.g., open frameworks, ceramic oxides, alloys, polymers, and so forth) can be operated against AC/conductive polymer electrodes.
This example describes hybrid electrodes including AC and an electrochemically active material as an additive. One additive used is PPy, which is a mixed-conducting polymer. This example demonstrates the use of an AC/PPy electrode in a wide variety of batteries. In addition, this example demonstrates the use of a lithium titanium phosphate, namely LiTi2(PO4)3 (“LTP”), as an additive in an AC/LTP electrode. Together, these implementations demonstrate the general approach of using AC/additive electrodes.
Synthesis of PPy was carried out at a relatively low temperature according to the following procedure: (1) Pyrrole (0.03 mol, 2 ml) was dispersed in 150 ml of de-aerated (N2) cold water (0° C.); (2) anhydrous Na2S2O8 (oxidant) (6.61 g, 0.03 mol) was dissolved in 50 ml of cold (0° C.) water in a reaction vessel including a magnetic stirring bar and added dropwise into the stirred oxidant solution; (3) reaction carried out for about 8 h at about 0° C. with moderate stirring; (4) precipitated PPy was filtered off and washed with cold de-ionized water; and (5) black PPy powder dried in vacuum at about 40° C. overnight to allow substantially full drying. The low temperature synthesis of PPy results in smaller particles with sizes less than about 500 nm. The smaller sizes, in turn, result in increased reactivity that improves the performance of PPy when used as an electrode. Specifically, cold-synthesized PPy shows improved electrochemical activity when used as an electrode, in comparison to PPy synthesized at room temperature.
As-synthesized PPy is fully oxidized. However, in order for PPy to impart a well-defined potential in a desired range, PPy should have a fractional charge state. Therefore, partial chemical or electrochemical reduction of the as-synthesized PPy is carried out before it is used effectively as an electrode additive. The mid-composition reaction potential of PPy is near 0 V versus SHE. Therefore, PPy can be chemically reduced using strong reducing agents such as sodium borohydride (NaBH4). Electrode slurries including PPy can be prepared and then exposed to aqueous solutions including reducing agents. For example, an AC/PPy slurry on a carbon cloth current collector can be dipped in 0.1 M NaBH4 to reduce the PPy component of the electrode to a desired charge state. The longer the duration of exposure to the reducing agent, the more the PPy component is typically reduced. Typical exposure times are from a few seconds to about 1 h, depending on the quantity of PPy and the quantity and strength of the reducing agent.
A full cell was implemented with an AC/PPy anode, an aqueous potassium-ion electrolyte (1 M potassium phosphate buffer, pH=1), and a Prussian Blue analogue (CuHCF) cathode. The anode included AC/PPy in a 9:1 mass ratio, without chemical reduction treatment.
Another full cell was implemented with an AC/PPy anode, an aqueous sodium-ion electrolyte (1 M sodium perchlorate, pH=7), and a sodium manganese oxide (“NMO”) cathode. The anode included AC/PPy in a 9:1 mass ratio, with chemical reduction treatment.
Another full cell was implemented with LTP as an electrochemically active. A pure LTP anode typically suffers from poor kinetics in aqueous lithium-ion batteries, which impedes cycling at high rates. However, its mid-composition reaction potential of about −0.5 V versus SHE render it desirable as an additive. By incorporating LTP in an AC electrode, an operating potential of the resulting LTP/AC hybrid electrode will be shifted to near the reaction potential of pure LTP. Here, the full cell included a lithium cobalt oxide (LiCoO2) cathode, an aqueous lithium-ion electrolyte (1 M lithium perchlorate, pH=7), and anode including AC/LTP in a 9:1 mass ratio, with partial chemical reduction of the LTP using NaBH4. The resulting aqueous lithium-ion battery using the AC/LTP anode can have full cell voltages of 1.5 V or more and can operate at high rates (see
While the invention has been described with reference to the specific embodiments thereof, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the invention as defined by the appended claims. In addition, many modifications may be made to adapt a particular situation, material, composition of matter, method, or process to the objective, spirit and scope of the invention. All such modifications are intended to be within the scope of the claims appended hereto. In particular, while the methods disclosed herein have been described with reference to particular operations performed in a particular order, it will be understood that these operations may be combined, sub-divided, or re-ordered to form an equivalent method without departing from the teachings of the invention. Accordingly, unless specifically indicated herein, the order and grouping of the operations are not limitations of the invention.
Cui, Yi, Huggins, Robert A., Pasta, Mauro, Wessells, Colin
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